To develop advanced heat transfer composites, new sets of unsymmetrical calamitic molecules with a coumarin unit at one end and a biphenyl group at the other end were synthesised. Their structural characterisation was investigated by routine techniques such as CHN analysis, and FT-IR, and 1D, and 2D NMR spectroscopic techniques. The liquid crystalline properties of these molecules were investigated by POM and DSC along with XRD techniques. All target compounds exhibited mesomorphic behaviour. The smectic C phase was seen for all the compounds. To enhance their thermal conductivities, conductive nanofillers, such as boron nitride nanosheets (BNNSs) and aluminium oxide nanoparticles Al2O3, were added to the synthesised liquid crystals. The LCnanocomposites exhibit excellent thermal conducting performance when a combination of BNNSs and Al2O3 nanoparticles were added to the liquid crystals. The thermal conductivity of the 4i-BN35-A15 nanocomposite was 1.7 W/m K compared to 0.3 W/m K for the pure liquid crystal compound 4i. [ABSTRACT FROM AUTHOR]